CN107434758A - A kind of method for synthesizing single bromo condensed-nuclei aromatics class compound - Google Patents

A kind of method for synthesizing single bromo condensed-nuclei aromatics class compound Download PDF

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CN107434758A
CN107434758A CN201710367448.0A CN201710367448A CN107434758A CN 107434758 A CN107434758 A CN 107434758A CN 201710367448 A CN201710367448 A CN 201710367448A CN 107434758 A CN107434758 A CN 107434758A
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condensed
nuclei aromatics
class compound
aromatics class
formula
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CN107434758B (en
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王力耕
余琴
陈璐焌
章华隆
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

A kind of method for synthesizing single bromo condensed-nuclei aromatics class compound, described method are carried out as follows：Using the condensed-nuclei aromatics class compound shown in formula I as substrate, alkali metal bromide is added, in the mixed solution of water and organic solvent, is slow added into ZnAl BrO3 ‑LDHs, 5~7h is reacted at 45~55 DEG C, after reaction terminates, the post-treated process of gained reactant mixture obtains single bromo condensed-nuclei aromatics class compound shown in formula II；Condensed-nuclei aromatics class compound, alkali metal bromide and ZnAl BrO shown in described formula I3 ‑The ratio between LDHs amount of material is 1:0.6~0.8:0.7~1.2, bromide reagent of the present invention is solid matter, cheap and easy to get, and environmentally friendly；Reaction condition is gentle；Convenient post-treatment, operation are simple；Atom utilization is high, and selectivity is high；Target product yield is high, and side reaction is few.

Description

A kind of method for synthesizing single bromo condensed-nuclei aromatics class compound
Technical field
The present invention relates to a kind of synthetic method of organic compound, and in particular to synthesizes single bromo condensed-nuclei aromatics class to one kind The method of compound.
Background technology
Condensed-nuclei aromatics halide is as a kind of important raw material or intermediate in essences such as medicine, agricultural chemicals, dyestuff and spices It is widely used in thin product chemistry.In all kinds of condensed-nuclei aromatics halide, bromine compounds because its reactivity is of a relatively high, and Bromine atoms are as a kind of leaving group easily sloughed, with the organic compound of bromine substitution for a long time in organic synthesis Since be considered as one kind have important value synthon either presoma, either in laboratory still in the industrial production Usage amount is larger, including the coupling of the keys such as C-C, C-N, C-O.In addition, they are either had radioactivity as medicine Diagnostic flag in drug therapy using extensive, closed so the method for preparing brominated organic compound is always chemist The content of note.
In existing document report, majority using bromine or NBS as bromine source come synthetic bromide for condensed-nuclei aromatics class chemical combination Thing.But using bromine it is intrinsic the shortcomings that be reaction in there is half bromo element to generate corrosive bromine product HBr, the theory of bromine Utilization rate only has 50%, the serious wasting of resources be present, and the reaction often needs to add the Louis such as metal break flour or bromide This acid is used as catalyst, further pollutes the Green Chemistry for not meeting existing promotion；Although NBS is kind of a safer bromo Reagent, but its preparation process is complicated, and preparation cost is higher, and generally makes in use along with special chemical auxiliary agent With so can not spread among actual production process.
Although prior art discloses the various methods for preparing single bromo condensed-nuclei aromatics class compound, these methods are universal There are one or more shortcomings such as：Severe reaction conditions, yield is relatively low, and the reaction time is longer, and selectivity of product is low, operation And post processing intricate operation etc..
The content of the invention
To overcome the shortcomings of the single bromo condensed-nuclei aromatics class compound of existing synthesis and shortcoming, it is an object of the invention to provide A kind of new method for synthesizing single bromo condensed-nuclei aromatics class compound.
The present invention uses following scheme：
A kind of method for synthesizing single bromo condensed-nuclei aromatics class compound, methods described are carried out as follows：With shown in formula I Condensed-nuclei aromatics class compound be substrate, add alkali metal bromide, in the mixed solution of water and organic solvent, then slowly plus Enter ZnAl-BrO3 -- LDHs, 5~7h is reacted at 45~55 DEG C, TCL tracking reaction process, after reaction terminates, gained reaction is mixed The post-treated process of compound obtains single bromo condensed-nuclei aromatics class compound shown in formula II；Condensed-nuclei aromatics shown in described formula I Class compound, alkali metal bromide and ZnAl-BrO3 -The ratio between-LDHs amount of material is 1:0.6~0.8:0.7~1.2,
Further, described alkali metal bromide is lithium bromide, sodium bromide, KBr, rubidium bromide or cesium bromide, is preferably KBr.
Further, the organic solvent is that the one or more in dichloromethane, toluene, ethyl acetate, acetonitrile, acetic acid are appointed The mixed solution of meaning ratio.
Further, the volumetric usage of the mixed solution of described water and organic solvent is with the condensed-nuclei aromatics class thing shown in formula I The amount of matter is calculated as 7.5~10ml/mmol.
Further, the volume ratio of described water and organic solvent is 1：13~19.
Further, the mixed solution of preferably described water and organic solvent is that volume ratio is 1:5:9 water, dichloromethane And the mixed solution of acetic acid.
Further, the reaction temperature of the condensed-nuclei aromatics class compound shown in preferably described formula I is 50 DEG C, and the reaction time is 6h。
Further, condensed-nuclei aromatics class compound, alkali metal bromide and the ZnAl-BrO shown in preferably described formula I3 -- The ratio between LDHs amount of material is 1:0.6:0.9.
More specifically, after reaction terminates, after described reactant mixture is using sodium sulfite solution washing, dichloromethane Extraction, merge organic phase, crude product is obtained after being concentrated under reduced pressure, gained crude product is with petroleum ether：Ethyl acetate=10~15:1 conduct Eluant, eluent, through column chromatography for separation, obtain single bromo condensed-nuclei aromatics class compound shown in target product formula II.
Compared with prior art disclosure, the beneficial effects of the present invention are：
Bromide reagent of the present invention is solid matter, cheap and easy to get, and environmentally friendly；Reaction condition is gentle；After locate Reason is convenient, and operation is simple；Atom utilization is high, and selectivity is high；Target product yield is high, and side reaction is few.
Embodiment
In order that creation feature, technological means, purpose and effect of the present invention are easy to understand, with reference to embodiment The present invention is described further and explains, but specific embodiment is not limitation of the present invention.
Embodiment 1
By pyrene (404mg, 2mmol), KBr (143mg, 1.2mmol), acetic acid 9ml, water 1ml, dichloromethane 5ml it is mixed Close solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath, ZnAl-BrO is slowly added in 15min in batches3 -- LDHs (1.8g, 1.8mmol), controlling reaction temperature are 50 DEG C, TCL tracking Reaction process, after reaction terminates, washed using sodium sulfite solution, then extracted, be associated with using dichloromethane (3 × 10ml) Machine phase, two medicine spoon column chromatography silica gels (200-300 mesh) are added in dichloromethane phase, are evaporated under reduced pressure away organic solvent, logical Cross column chromatography (petroleum ether：Ethyl acetate=15:1 is used as eluant, eluent) isolated target product 383mg.White solid, yield 68%.
Characterize data：Fusing point：148-150.1H NMR(500MHz,CDCl3)δ:8.46 (d, J=9Hz, 1H), 8.25 (t, J =8Hz, 3H), 8.20 (d, J=9Hz, 1H), 8.12 (d, J=9Hz, 1H), 8.08-8.02 (m, 3H)
Embodiment 2
By pyrene (404mg, 2mmol), lithium bromide (104mg, 1.2mmol), acetic acid 9ml, water 1ml, dichloromethane 5ml Mixed solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath, Slowly add ZnAl-BrO in batches in 15min3 -- LDHs (1.8g, 1.8mmol), controlling reaction temperature be 50 DEG C, TCL with Track reaction process, after reaction terminates, washed using sodium sulfite solution, then extracted using dichloromethane (3 × 10ml), merged Organic phase, two medicine spoon column chromatography silica gels (200-300 mesh) are added in dichloromethane phase, are evaporated under reduced pressure away organic solvent, Pass through column chromatography (petroleum ether：Ethyl acetate=15:1 is used as eluant, eluent) isolated target product 371mg.White solid, production Rate 66%.
Characterize data：Fusing point：148-150.1H NMR(500MHz,CDCl3)δ:8.46 (d, J=9Hz, 1H), 8.25 (t, J =8Hz, 3H), 8.20 (d, J=9Hz, 1H), 8.12 (d, J=9Hz, 1H), 8.08-8.02 (m, 3H)
Embodiment 3
By pyrene (404mg, 2mmol), sodium bromide (124mg, 1.2mmol), acetic acid 9ml, water 1ml, dichloromethane 5ml it is mixed Close solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath, ZnAl-BrO is slowly added in 15min in batches3 -- LDHs (1.8g, 1.8mmol), controlling reaction temperature are 50 DEG C, TCL tracking Reaction process, after reaction terminates, washed using sodium sulfite solution, then extracted, be associated with using dichloromethane (3 × 10ml) Machine phase, two medicine spoon column chromatography silica gels (200-300 mesh) are added in dichloromethane phase, are evaporated under reduced pressure away organic solvent, logical Cross column chromatography (petroleum ether：Ethyl acetate=15:1 is used as eluant, eluent) isolated target product 377mg.White solid, yield 67%.
Characterize data：Fusing point：148-150.1H NMR(500MHz,CDCl3)δ:8.46 (d, J=9Hz, 1H), 8.25 (t, J =8Hz, 3H), 8.20 (d, J=9Hz, 1H), 8.12 (d, J=9Hz, 1H), 8.08-8.02 (m, 3H)
Embodiment 4
By pyrene (404mg, 2mmol), KBr (143mg, 1.2mmol), acetic acid 9ml, water 1ml, dichloromethane 5ml it is mixed Close solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath, ZnAl-BrO is slowly added in 15min in batches3 -- LDHs (1.8g, 1.8mmol), controlling reaction temperature are 45 DEG C, TCL tracking Reaction process, after reaction terminates, washed using sodium sulfite solution, then extracted, be associated with using dichloromethane (3 × 10ml) Machine phase, two medicine spoon column chromatography silica gels (200-300 mesh) are added in dichloromethane phase, are evaporated under reduced pressure away organic solvent, logical Cross column chromatography (petroleum ether：Ethyl acetate=15:1 is used as eluant, eluent) isolated target product 360mg.White solid, yield 64%.
Characterize data：Fusing point：148-150.1H NMR(500MHz,CDCl3)δ:8.46 (d, J=9Hz, 1H), 8.25 (t, J =8Hz, 3H), 8.20 (d, J=9Hz, 1H), 8.12 (d, J=9Hz, 1H), 8.08-8.02 (m, 3H)
Embodiment 5
By pyrene (404mg, 2mmol), KBr (143mg, 1.2mmol), acetic acid 9ml, water 1ml, dichloromethane 5ml it is mixed Close solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath, ZnAl-BrO is slowly added in 15min in batches3 -- LDHs (1.8g, 1.8mmol), controlling reaction temperature are 55 DEG C, TCL tracking Reaction process, after reaction terminates, washed using sodium sulfite solution, then extracted, be associated with using dichloromethane (3 × 10ml) Machine phase, two medicine spoon column chromatography silica gels (200-300 mesh) are added in dichloromethane phase, are evaporated under reduced pressure away organic solvent, logical Cross column chromatography (petroleum ether：Ethyl acetate=15:1 is used as eluant, eluent) isolated target product 371mg.White solid, yield 66%.
Characterize data：Fusing point：148-150.1H NMR(500MHz,CDCl3)δ:8.46 (d, J=9Hz, 1H), 8.25 (t, J =8Hz, 3H), 8.20 (d, J=9Hz, 1H), 8.12 (d, J=9Hz, 1H), 8.08-8.02 (m, 3H)
Embodiment 6
By pyrene (404mg, 2mmol), KBr (143mg, 1.2mmol), acetic acid 6ml, water 1ml, dichloromethane 4ml and second Acetoacetic ester 5ml mixed solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred to heated at constant temperature magnetic force and stir Mix in water-bath, slowly add ZnAl-BrO in batches in 15min3 -- LDHs (1.8g, 1.8mmol), controlling reaction temperature For 25 DEG C, TCL tracking reaction process, after reaction terminates, washed using sodium sulfite solution, then using dichloromethane (3 × 10ml) extract, merge organic phase, two medicine spoon column chromatography silica gels (200-300 mesh) are added in dichloromethane phase, are evaporated under reduced pressure out Organic solvent is removed, is passing through column chromatography (petroleum ether：Ethyl acetate=15:1 is used as eluant, eluent) isolated target product 377mg.White solid, yield 67%.
Characterize data：Fusing point：148-150.1H NMR(500MHz,CDCl3)δ:8.46 (d, J=9Hz, 1H), 8.25 (t, J =8Hz, 3H), 8.20 (d, J=9Hz, 1H), 8.12 (d, J=9Hz, 1H), 8.08-8.02 (m, 3H).

Claims (9)

  1. A kind of 1. method for synthesizing single bromo condensed-nuclei aromatics class compound as shown in formula II, it is characterised in that described preparation Method is：Using the condensed-nuclei aromatics class compound shown in formula I as substrate, alkali metal bromide is added, in the mixed of water and organic solvent Close in solution, be slow added into ZnAl-BrO3 -- LDHs, 5~7h is reacted at 45~55 DEG C, after reaction terminates, gained reaction is mixed The post-treated process of compound obtains single bromo condensed-nuclei aromatics class compound shown in formula II；Condensed-nuclei aromatics shown in described formula I Class compound, alkali metal bromide and ZnAl-BrO3 -The ratio between-LDHs amount of material is 1:0.6~0.8:0.7~1.2,
  2. A kind of 2. method for synthesizing single bromo condensed-nuclei aromatics class compound as claimed in claim 1, it is characterised in that：Described Alkali metal bromide is lithium bromide, sodium bromide, KBr, rubidium bromide or cesium bromide.
  3. A kind of 3. method for synthesizing single bromo condensed-nuclei aromatics class compound as claimed in claim 1, it is characterised in that：It is described to have Solvent is the mixed solution of dichloromethane, toluene, ethyl acetate, acetonitrile, one or more arbitrary proportions in acetic acid.
  4. A kind of 4. method for synthesizing single bromo condensed-nuclei aromatics class compound as claimed in claim 1, it is characterised in that：Described The cumulative volume dosage of the mixed solution of water and organic solvent is calculated as 7.5~10ml/ with the amount of the condensed-nuclei aromatics class material shown in formula I mmol。
  5. A kind of 5. method for synthesizing single bromo condensed-nuclei aromatics class compound as claimed in claim 1, it is characterised in that：Described The volume ratio of water and organic solvent is 1：13~19.
  6. A kind of 6. method for synthesizing single bromo condensed-nuclei aromatics class compound as claimed in claim 3, it is characterised in that：Described The mixed solution of water and organic solvent is that volume ratio is 1:5:The mixed solution of 9 water, dichloromethane and acetic acid.
  7. A kind of 7. method of synthesis list bromo condensed-nuclei aromatics class compound as described in claim 1~6, it is characterised in that：Institute The reaction temperature of condensed-nuclei aromatics class compound shown in the formula I stated is 50 DEG C, reaction time 6h.
  8. A kind of 8. method of synthesis list bromo condensed-nuclei aromatics class compound as described in claim 1~6, it is characterised in that：Formula I Shown condensed-nuclei aromatics class compound, alkali metal bromide and ZnAl-BrO3 -The ratio between-LDHs amount of material is 1:0.6:0.9.
  9. A kind of 9. method for synthesizing single bromo condensed-nuclei aromatics class compound as claimed in claim 1, it is characterised in that：Reaction knot Shu Hou, after described reactant mixture is using sodium sulfite solution washing, dichloromethane extraction, merges organic phase, be concentrated under reduced pressure Crude product is obtained afterwards, and gained crude product is with petroleum ether：Ethyl acetate=10~15:1 is used as eluant, eluent, through column chromatography for separation, obtains Single bromo condensed-nuclei aromatics class compound shown in target product formula II.
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